Process for breaking petroleum emulsions



,1 M. DE GROOTE ET AL 2,574,543

PROCESS FOR BREAKING PETROLEUM EMULSIONS F1165 Nov. 28, 1949PHENOL-ACETYQ ENE C H O RESIN 100 4 1007 INVENTORS, O MELVIN DEGRO TEBERNHRRD K515 R By [0% 79M A TT'ORNE K Patented Nov. 13, 1951 UNITEDSTATES PATENT OFFICE PROCESS FOR BREAKING PETROLEUM EMULSIONSApplication November 28, 1949, Serial No. 129,709

8 Claims.

The present invention relates to processes or procedures particularlyadapted for preventing, breaking, or resolving emulsions of thewaterin-oil type; and particularly petroleum emulsions. The presentapplication is a continuation-in-part of our co-pending applicationsSerial Nos. 8,722 and 8,7 3, both filed February 16, 1948, and ourco-pending appl cation Serial No. 59,768, filed November 12, 1948. Theseapplications have now matured into Patents Nos. 2,499,365 and 2,499,366,dated March 7, 1950, and 2,560,333, dated July 10, 1951.

Complementary to the above aspectof our invention is our companioninvention concerned with the new chemical products or compounds used asthe demulsifying agents in the herein described processes or procedures,as well as the application of such chem cal compounds, products, and thelike, in various other arts and industries, along with methods formanufactur ing said new chemical products or compounds which are ofoutstanding value in demulsification. See our co-pending applicationSerial No. 129,710, filed November 28, 1949.

' In our copending application above mentioned, Serial No. 59,768, filedNovember 12, 1948, the invention is concerned with a process forbreaking petroleum emulsions of the water-inoil type, characterized bysubjecting the emulsion to the action of a demulsifier includinghydrophile synthetic products; said hydrophile synthetic products beingoxyalkylation products of.

(A) An alpha-beta alkylene oxide having not more than 4 carbon atoms andselected from the class consisting of ethylene oxide, propylene oxide,butylene oxide, glycide and methylglycide; and

(B) An oxyalkylation-susceptible, fusible, or-

ganic solvent-soluble, water-insoluble, phenolic resin; said resin beingderived at least in partby reaction with an acetylenic hydrocarbon so asto introduce an altered acetylenic radical as the linking structurebetween phenolic nuclei; said oxyalkylated resin being characterized bythe introduction into the resin molecule of a plurality of divalentradicals having the formula (R10) 11."

in which R1 is a member selected from the class consisting of ethyleneradicals, propylene radicals, butylene radicals, hydroxypropylene radi-'cals, and hydroxybutylene radicals, and n is a numeral varying from 1 to20; with the proviso that at least 2 moles of alkylene oxide beintroduced for each phenolic nucleus.

The present invention is sub-generic tothe invention described in theaforementioned pending application Serial No. 59,768, with the provisothat the alkylene oxide, instead of being selected from the five oxidesmentioned, is limited to the use of two oxides, i. e., ethylene oxideand propylene oxide, with the further proviso that both oxides must beused in each instance, and in addition, the final product of re actioncorrelated to the percentage weight of initial reactants must comewithin the trapezoidal area defined by points I, 2, 3 and 4 on theattached figure, all of which is conventional repre-:- sentation.

Demulsification, as contemplated in the present application, includesthe preventive step of com-' mingling the demulsifier with the aqueouscomponent which would or might subsequently become either phase of theemulsion in the absence of such precautionary measure. Similarly, suchdemulsifier may be mixed with the hydrocarbon component.

Since the present invention is cogeneric to the inventions described incertain of our co-pending applications, previously noted, andparticularly Serial No. 59,768, filed November 12, 1948, and since thediiierence rests in the nature of the oxyalkylation step, it obviouslyfollows that the preparation of the initial raw materials, i. e., theresins, is identical with what is said in Serial No. 59,768, filedNovember 12, 1948, now Patent 2,560,333, granted July 10, 1951, andreference is made to that patent for a full and complete description ofthe resin and in particular, to Examples 1 through 24, 11) through 101),and 10 through 50 for specific examples of suitable resins.

Having obtained a suitable resin of the kind described, such resin issubjected to treatmentwith a low molal reactive alpha-beta olefineoxide, so as to render the product distinctly hydrophile in nature, asindicated by the fact that it becomes self-emulsifiabl-e or miscible orsoluble in water, or self-dispersibla'or has emulsifying properties.

As previously stated, the present invention is sub-generic to thatdescribed in our co-pending application Serial No. 59,768, filedNovember 12, 1948, in the sense that the present invention is limited tothe use of both ethylene oxide and propylene oxide, so that'the finalcompositions of matter come within the composition approximately definedby the trapezoidal area I 2, 3, and 4 of the chart in the accompanyingdrawing.

The oxyalkylation of resins of the kind from which the products used inthe practice of the present invention are prepared is advantageouslycatalyzed by the presence of an alkali. Useful It may be necessary toallowfor't-he. acidityofj a resin in determining the amount 'of alkalinecatalyst to be added in oxyalkylation. For instance, if a nonvolatilestrong acid. such as sulfuric acid is used to catalyze theresinification reaction, presumably after being converted into asulfonic acid, it may be necessary and is usually advantageous. to addan amountof-alkali equal stoichiometrically' to such' 'acidity, andinclude added alkali over and. above. this amount as the alkalinecatalyst;

It isadvantageous to:conducttheoxyethyla-v tion.in pr-esenceof: an inertsolvent suchas xylene, cymene'; decalin; ethylene glycol 1 diethylether;diethyleneglycol diethylether,: or the like, althouglr with manyres-ins. the oxyalky-lation proceeds satisfactorily without. asolvent.Since xylene isrcheap' and maybe permitted tobe present in the finalproduct used as a demulsi-fier, it is our preference to use" xylenelihisis particularly true '.l1'l. the manufacture? of products from low-stageresins, i. e., of-:3 and up to andincluding 7 units per molecule.

If axylene, solution is used in: anautoclave as hereinafter indicated,the pressure readings of course represent total pressure, that is, thecombined pressure due to xylene and also due to ethylene oxide orwhatever other oxyalk-ylating agent is used. Under-such circumstances itmay be. necessary attimes to use; substantial pressures. to obtaineffective. results, for instance, pressures up to 300 pounds along with;correspondingly hightemperatures, if required.

However, even; in the instance of-high-melting resins, a solvent-such asxylene can be eliminated in either one of two. ways: After'theintroduction of approximately 2 or 3 moles of ethylene oxide, forexample, per phenolic nucleus, there is a definite dropin the hardnessand melting point of the resin. At this stage, if xylene or a. similarsolvent has been added it can be eliminated by distillation (vacuumdistillation if desired) and the subsequent intermediate, beingcomparatively soft and solvent-free, can be reacted furth-er in theusual manner with ethylene oxide or some oth r suitable reactant.

' Another procedure is to continue the reaction to completion with suchsolvent present and then eliminate the solvent by distillation in thecustomary manner.

' Attention is directed to the fact that the resins herein describedmust be fusible or soluble in an organic solvent. Fusible resinsinvariably are soluble in one'or more organic solvents, such asgthosementioned elsewh re herein. It is to be emphasized, however, that theorganic solvent employed to indicate or assure that the resin meets thisrequirement need not be the one used in oxyalkylation. Indeed solventswhich are susceptible to oxyalkylation are included in this group oforganic solvents. Examples of such solvents are alcohols and alcohol-cthl's,

In a,

However, where a resin is soluble in an organic solvent, there areusually available other organic solvents which are not susceptible tooxyalkylation, useful for the oxyalkylation step. In any event, theorganic solvent-soluble resin can be finelypowdered for instance,,to 109110.200 mesh,

and a slurry Or -suspension prepared: in xylene or the like, andsubjected to oxyalkylation. The

fact that the resin is soluble in an organic solvent, or the fact thatit is fusible, means that it consists of separate molecules.Phenol-aldehyde resins of the type herein specified possess reactivehydroxyl. groups and are oxyalkylation-suscep- -tible.

[Considerable of; what is said immediately hereinafter is concerned withthe ability to vary the hydrophile properties of the compounds used inthe process from minimum hydrophile properties. to maximum hydrophileproperties.

Even more remarkable, and equally difificult to explain,are.the.versatility..and utility of these. compounds as. .one goes fromminimum hydrophile property to. ultimate maximum hydrophileproperty-",For

instance, minimum hydrophileproperty may. be described roughly as thepointwher're. two..,ethy;leneoxy radicals or moderately .in excessthereof are introduced per phenolic .hydroxyl. Such minimum hydrophileproperty or sub-surface"- activity or. minimumv surface-activity: meansthat the product shows at least emulsifying. properties orself-dispersion in cold or even in. Warm. dis! tilled water (15 to 40C.) in concentrations of Thesev materials... are. generally more solublein cold waterlthanwarm'water, and

may even be very insoluble..in boiling water Moderately hightemperatures-aidin reducing the. viscosity of the solute underexamination. Some.- times if one continues .to shake ahot solution;-even though cloudy .or containing .an insoluble. phase, one. finds thatsolution takes. place to giye a homogeneous phase asthemixture cools...Such. self-dispersion tests are conductedin the absence of. an insolublesolvent. I

When the hydrophile-hydrophobic. balance. is. above theindicatedminimum.(2. moles of ethylene oxide per phenolic nucleus or the. equivalent).but. insufficient togive a sol as.describedlimniediateht preceding,then, and in. that event .hydrophile properties are indicated by thefact. that one. can produce an emulsion by having present. 10% to. %.ofaninert. solvent suchasxylene... All that. one need to do is to have axylene solution .within.

the range of 50 to 90 partsby weight. of oxyalkylated derivatives and 50to 10 parts. by weight of.

xylene and mix such solution with one, two or.

threetimes its volume of distilled. water and shake vigorously so as toobtain an emulsion which may be of the oil-in-water type or. the.water-in-oil type (usually the former) but, in any eventdue tothehydrophile-hydrophobe. balance. of. the

' oxyalkylated derivative. 'We prefer simply to use thexylene dilutedderivatives, which are described elsewhere, for this test ratherthanevaporate the solvent and employ any more.- elaborate. tests, if

the solubility is not sufficient. to. permit the simple sol test inwater previously noted. Ifthe product is not readilyv Water soluble.

may be, dissolved in ethyl or methyl alcohol, ethyl- 1: ing-'(i.e., ifthe oxyalkylated product'is a liquid or a liquid solutionself-emulsifiable), such sol or dispersion is referred to as at leastsemi-stable in the sense that sols, emulsions, or dispersions preparedare relatively stable, if they remain at least for some period of time,for instance minutes toutwo hours, before showing any marked separation.Such tests are conducted at room temperature (22 C.). Needless to say, atest can be made in presence of an insoluble solvent such as 5%+-to.-l5'% of xylene, as noted in previous examples. If such mixture, i.e., containing a waterinsoluble solvent, is at least semi-stable,obviously thesolvent-free productwould be even more so. Surface-activityrepresenting an advanced hydrophile-hydrophobe balance can also bedetermined by the use of conventional measurements hereinafterdescribed. One outstanding characteristic propertyindicatingsurface-activity in a material is the. ability to form a permanent foamin dilute aqueous solution, for example, less than 0.5%, when in thehigher oxyalkylated stage, and to forinan emulsion in the lower andintermediate stages of oxyalkylation.

Allowance must be made for the presence of a solvent in the finalproduct in relation to the hydrophile properties of the final product.The principle involved in the manufacture of the herein-coritemplatedcompounds for use as demulsifyin'g'agents, is based on the conversion ofa hydrophobe or non-hydrophile compound or mixture of-compounds intoproducts which are distlnctly hydrophile, at least to the extent thatthey solutions or sols which show typical properties comparable toordinary surface-active agents. Such conventional surface-activity maybe measured'by determining the surface tension and the interfacialtension against paraffin oil or the like. Atthe'initial and lower stagesof oxyalkylation, surface-activity is not suitably determined in thissame manner but one may employ an emulsification test. Emulsions comeinto existence as a rule through the presence of a surface-activeemulsifying agent. Some surface-active emulsifying agents such asmahogany soap may produce a water-'in-oil emulsion or an oil-in-wateremulsion depending upon the ratio of the two phases, degree ofagitation, concentration of emulsifying agent, etc.

The same is true in regard to the oxyalkylated resins herein specified,particularly in the lower is --then mixed with l-3 volumes of water andshaken to produce an emulsion. The amount of xylene is invariablysufficient to reduce even a tacky resinous product to a solution whichis readily dispersible. The emulsions so produced 6, are usuallyxylene-in-water emulsions (oil-inwater type) particularly when theamount of distilled water used is at least slightly in excess of thevolume of xylene solution and also if shaken vigorously. At times,particularly in the lowest stage of oxyalkylation, one may obtain awaterin-xylene emulsion (water-in-oil type) which is apt to reverse onmore vigorous shaking and furemulsification test. In a few instances,the resin may not be sufiiciently soluble in xylene alone but mayrequire the addition of some ethylene glycol diethylether as describedelsewhere. It isunderstood that such mixture, or any other similarmixture, is considered the equivalent of xylene for the purpose of thistest.

In many cases, there is no doubt as to the presence or absence ofhydrophile or surface-active characteristics in the products used inaccordance with this invention. They dissolve or disperse in water; andsuch dispersions foam readily. With borderline cases, i. e., those whichshow only incipient hydrophile or surface-active property(sub-surface-activity) tests for emulsifying properties orself-dispersibility are useful. that a reagent is capable of producing adispersion in water is proof that it is-distinctly hydrophile. Indoubtful cases, comparison can be made with the butylphenol-formaldehyderesin analog wherein 2 moles of ethylene oxide have been introduced foreach phenolic nucleus.

The presence of xylene or an equivalent waterinsoluble solvent may maskthe point at which a solvent-free product on mere dilution in a testtube exhibits self-emulsification. For this reason, if it is desirableto determine the approximate point where self-emulsification begins,then it is better to eliminate the xylene or equivalent from a smallportion of the reaction mixture and test such portion. In some cases,such xylene-free resultant may show initial or incipent hydrophileproperties, whereas in presence of xylene such properties would not benoted. In other cases, the

-fll'St objective indication of hydrophile properties may be thecapacity of the material to emulsify an insoluble solvent such asxylene. It is to be emphasized that hydrophile properties hereinreferred to are such as those exhibited by incipient self-emulsificationor the presence of emulsifying properties and go through the range ofhomogeneous dispersibility or admixture with water even in presence ofadded water-insoluble solvent and minor proportions of commonelectrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsiiication test may be used todetermine ranges of surface-activity and that such emulsification testsemploy a xylene solution. Stated another way, it

is really immaterial whether a xylene solution produces a sol or whetherit merely produces an emulsion.

In light of what has been said previously in regard to the variation ofrange of hydrophile properties, and also in light of .What has been Thefact widexvariation; in ,thecamountzpf :alk-ylenel.oXide,.

employed; as clong'siassit is at least..-2 moles perv-: phenolicnucleus, for producing products useful-1 for the practice of this.dnventionhrAnother -c, variation is the molecular sizenrofitheresinichainq; resulting from reactions-between the :difunctional phenoland the :aldehyde; such as formaldehyde. Itfi's we1l" knOWn:.thatthezsize-"andnature or structure" of zthe iiresin-u polymer, obtainedvaries. somewhat withrtheuconditions of .reaction; :the l proportions ofreactants, the'nature, of the catalyst, etch H In .our co-pending:application Serial No.8,l30, file'dFebruary .16, 1948,'-noW-abandoned,=in regard toezphenolealdehyde resins xperz'se; .we said .as follows:

Based on .molecular weight, determinations, most of the resinsprepared,'as herein describedyr: particularly in the absence ofasecondary heating step,"contain 3 to 6 or 7'7 phenolic nuclei vWith'aapproximately 4 or'5 /g'nuclei as:an-; average. More drastic conditionsof .resinification yield '1; resins of greater chain length.Such.moreiin-" tensive resinification-is a, conventional procedure andmayi lee-employed; :if "desired." Molecular weight, of 'course',iismeasured by: any suitable '30 procedure, particularly by cryoscopicmethods, but using the. same. reactants and using 'jl'llOX'Bdrasticiiconditiom 10f resinification, one usually finds :that highermolecularpweights are indicated byhigher melting points of 'the'rresinsand a 35. tendency to decreasedsolubility. See what has been saidelsewhere herein inregard to a secondary step involving the. heating-ofa resin with orwithout the use1 of"vacuum.-:

If such resins are 'given anTafter-treatmentAO with acetylene, and suchtreatment; in :orderwrr to meet the requisites "herein" stated-,xrjoinsat least two resin molecules rtogeth'er by'a linkage such .as thefollowing:."

H -H then, of course, there is an increase in molecular i weight of atleast. double thetprevious values Similarly; resins prepared inthemanner of the 59 commercial" product, K018Sin,"Sllch ias an iamylgthexyl or octyl Koresin, yield relatively soft or tacky resins, in whichthere are'lonlyf3 or 4 or. possibly 5 units.' Such resins can 'be'treated further with formaldehyde in the manner 'de scribed so as togive resins of higher molecular weights than the initial resin;Therefore, without attempting to elaborate too closely, 'We simplydesire to point out that the range of molecular weight of the variousresins herein c0 contemplated may go-anywhere from a low range resinhaving 3 to 6 or 7 phenolic nucleiwith ap'- proximately-4 to'5 nuclei asan averageyupto: ratios double these valuesor inexcess thereof."

We desire to emphasize that the resins, prior 5:. to oxyethylation, mustbe fusible and organic solvent-soluble." They are, of course,essentially hydrophobe in character? The final product obtained byoxyalkyla'tion 'must' possess hydromaybe tworesinificatione:procedures;z?onezain ::maybe treatedswith an aldehyde;The:.-most sing paragraph which appears :in .our aforeme'n' eat onceinto 'a more complex structure during their;

7 8;: 7 (now abondonedrpwe: maveizpointedsout' that 1111 solubilizationmayrarisein a number of iwaysgsand particularly. ;.due totcross-linking; sin thearesi ification process,:or: in the oxyalkylation'processm Therefore; everything that t has been'saidin 5.0111"aforementioned" :coepending application Seri Non-8,730v in :regard to 2the. resinificationiprocess also applies inthe" instant applicationrasfarixasm producingresins from phenols and acetylenegoesau ion the:onerhand, sin :comparison :Withi resins Id rived froinphenols:and-aldehyde; on theiotheitu hand; 7 7 r V In somecases;however; thei-situation einnthe instant case iscomplicated;byithefactuthatithe volving an aldehyde. and "lthel other:involving acetylene. In oth'er words; a ":phenolraldehy'de resin may besubjected"to':treatmene'withi'ace ylene; or; .invierselyya'phenol-acetylene iireslnh practical procedure is simply to take'anymixture of phenols and treat it vvithacetylene or thei equivalentytp':obtain a fusible; organic :solvents e soluble resin; or, if desired'ppreparera' phenolel ialdehyde- "resinrr and treat :such" resinsuwith hacetylene. 7 As far? as the preparation :of :ther .phenolaldee hyderesins go' for' subsequent";afteretreatment with acetylene, attentioniscalled'to thefollowtioned co-pending zapplicationvserial NoefiflfiWe-have pointed outrtha't eitheran alkaline or "acid catalyst isadvantageously/used in pree paring the resin. A combination ofcatalystsais sometimes used in .two StagGS'FEfOI instance; ;an alkalinecatalyst :is sometimes employedina first stage, followed "byneutralization and addition act a small-amount of acid catalyst'in asecond stage: It is generally believed that even in thepresence of analkaline catalystpthe'number 'of moles-of aldehyde, such as:formaldehyde, must be "greater than themoles of phenoliremployedi'n'order :to i introduce methylol groups in the; intermediate 2 stage:There is "no indication that-:such' groups appear in the .final'resin;if preparedby-thefuse of an .acid catalyst: -'"It is possiblethatsuchrgroups may appear in vthe'finished resins prepared-sol 1y with analkaline -catalyst;- but we have-never been able to confirm thisifact in'an examina'tion ,of a large number-of; resins prepared byvour-r selves.F Our preference, however;- is :to-:use-an acidg-catalyzed I resin,particularly: employing *a formaldehyde-to -pheno1 ratio of 0.95 to122.0; and; as far as we have been able to determine;-such resins arefree from methylolgroupsmiAs a mat-r ter of fact, it is probablethat-in, acid-catalyzed resinifications'; the "methylol' structure -ma-yap! pear only momentarily *atthe very-beginningiof the reaction; and inall probability; is converted intermediate stage.

One procedure which canbe employedvinrthe-i; use of a new resintoprepare products for 21156 in'the process of the invention is *todetermine @the'hydroxyl value by the"verley Bolsing-method orits'equivalent; 'Ihe resin asjsuch OrIinIthe formof a solutionasdescrib'ed; was ithen'treated with a mixture'of ethyleneoxidet'andrpropylene oxidev "in presence. of10.5%"'toit2%fiofrisodluinphobe orsurface-active-properties.or sub-suriacee =7 e'methylate as acatalyst inistep-wise' fashions:

active '.properties;;" as hereini described. :r'For :1" practicalpurposes, this means that there'wmustiv' be; aniamount of cross-linkingsufficient to give insoluble L products." 1 In ounce-pending r application'; :Serial -No'.: 8,730'fi filed' February: 16, "1948 L 7 '4. Our,:preferenceiis to iusei'therpropylene oxide The ratios of propyleneoxide andiethylene oxide employed correspond-to the ratios;:in thelimiting points I on the triangular graph:'or: chart initheaccompanying-drawing, to wit,.points5l-, 2, 3 and wer and then theethylene oxide. If the resulting products meet therequirements as tosurface-acti ve properties noted elsewhere, the resin is entlrelysatisfactory. In some instances, such tests are best conducted by addingethylene oxide first and then propylene oxide, or adding amixture of thetwo alkylene oxides at the same time.

Attention is directed to the fact that in the subsequent examplesreference is made to the step-wise addition of the alkylene oxide, suchas ethylene oxide. It is understood, of course, there is 'no objectionto the continuous addition of alkylene oxide until the desired stage ofreaction is" reached. In fact, there may be less of a hazard involvedand it is often advantageous to add the alkylene oxide, or mixture,slowly in a continuous stream and in such amount as to avoid exceedingthe higher pressures noted in the various examples or elsewhere.

T It may be well to emphasize the fact that when resins are producedfrom difunctional phenols and some of the higher aliphatic aldehydes,such as acetaldehyde, the resultant is a comparatively soft orpitch-like resin at ordinary temperatures. Such resins becomecomparatively fluid at 110 to 165 C., as a rule, and thus can be readilyoxyalkylated, without the use of a-solvent.

What has been said previously is not intended to'sug'gest that anyexperimentation is necessary tddetermine the degree of oxyalkylation,and particularly oxyethylation. What has been said previously issubmitted primarily to emphasize the? fact that these remarkableoxyalkylated resins having surface-activity show unusual properties asthehydrophile character varies from a minimum to an ultimate maximum.One should nit'underestimate the utility of any of these products in asurface-active or sub-surface-active range without testing them fordemulsification. A few simple laboratory tests which can be conducted ina routine manner will usually give all the information that is required.

For instance, a simple rule to follow is to prepare a resin having atleast 3 phenolic nuclei and being organic solvent-soluble. Oxypropylatesuch resin, using the six following ratios of propylene oxide perphenolic unit equivalent: 2 to ,1; 4 to 1; 6 to 1; 10 to 1; to '1; and.-jto 1. Each oxypropylated sample thus obtained is treated with ethyleneoxide in three different ratios, the first ratio being where the amountof ethylene oxide on a molal basis is just one-half that of thepropylene oxide used in oxypropylation; the second ratio being where theamount of ethylene oxide is just equal to the amount of propylene oxideused on a molal basis; and the final ratio being where the amount ofethylene oxide used is 50% more than the propylene oxide used on a molalbasis.

This gives a total of 18 samples, covering a Q fairly wide range.Prepare 0.5% and 5.0% solutions in distilled water, as previouslyindicated. A mere'examination of such series will reveal generally anapproximate range of minimum hydrophile character, moderate hydrophilecharacter, and maximum hydrophile character. If any one of the threevariations of the 2 to l propylene oxide ratio does not show minimumhydrophile effect by test of the solvent-free product, then one shouldtest the capacity of the three variants to form an emulsion when mixedwith xylene or otherinsoluble solvent. If neither test on the threevariants shows the required minimum hydrophileproperty, furtherexamination is re-.-.

10 quired in regard to the other members of the series. Moderatehydrophile character should be shown by either a Q to 1' or 10 to 1ratio, based on the combined amount of both oxides. Such mod eratehydrophile character is indicated by the fact that the sol in distilledwater within the previously mentioned concentration range is a permanenttranslucent sol, when viewed in a comparatively thin layer, forinstance, the depth of a test tube.

See also 'what has been said previously in reent invention is concernedwith the use of both propylene oxide and ethylene oxide. By using acomparatively large amount of ethylene oxide and a comparatively smallamount of propylene oxide (assuming that the selected combination comeswithin the limits hereinafter specified) one can obtain a product whichgives ultimate hydrophile character. However, ultimate hydrophilecharacter of itself is not necessarily significant, because obviously, aresin treated with 15 to 20 or 30 moles of ethylene oxide per phenolicunit will be more water-soluble than a similar combination whereone-fifth or one-third or onehalf of the ethylene oxide is replaced bypropylene oxide.

Therefore, even though the compounds or derivatives herein described aresurface-active or subsurface-active from the standpoint described inco-pending application Serial No. 82,704, filed March 21, 1949 (nowPatent No. 2,499,370 dated March 7, 1950), yet the limits are carefullyset out by another set of factswe describe in the text immediatelyfollowing. These limits make it extremely simple to prepare combinationsof resins with propylene oxide and ethylene oxide which will meet theherein described requirements.

After preparing a large number of oxyethylated derivatives of thesevarious resins, as described in Serial No. 82,704, filed March 21, 1949,and subsequently subjecting them to oxypropylation, we have found thatnot infrequently, and in fact, in many cases, the derivatives ormixtures obtained by such combined treatment, yielded products ofgreater value for many uses and particularly for some cases the changefrom slow speed agitation,

for example, in a laboratory autoclave with a stirrer operating at aspeed; .o f 60 to 20 R. P. M., to high speed agitation withthe'stirreroperating at'250 to 350 R. P. M., reduces the time required foroxyalkylation by one-half to two-thirds. Frequently, xylene-solubleproducts which give insoluble products by procedures employingcomparatively slow speed agitation, give suitable hydrophile productswhen produced by similar procedure, butwith high speedagitation, as aresultL we believe, of the reduction in the time required with"consequent" elimination or curtailment of opportunity for curing oretherization. Even if the -formation of: an insoluble product is notinvolved-,it is frequently advantageousto speed up the reaction, therebyreducing production time, by increasing agitating speed. In large scaleoperations, we have demonstrated that economi= for demulsification ofwater-in-oil emulsions, and

for that matter, for otherpurposes, one should make a completeexploration of the wide variation hydrophobe-hydrophile balance; aspreviously'referred to. It has been stated, further-- more, that thishydrophobe-hydrophile balance of the oxyalkylated resins isimparted, asfar as the range ofvariationgoes, to agreater or lesser extent totheherein described derivatives; This means that one" employing the presentinvention should take the choice of the most suitable derivativeselected-iroma number of representative compounds, --thus; not onlyshould a variety of resinsbe prepared exhibiting a variety ofoxyalkylations, notonly from the-standpoint of a varying ethyleneoxide-propylene oxide V (a) Temperaturerise or drop, if

('12) Amount of cooling 'water or other means;

sure to cause the oxideto-moveintothei'autd clave; v '1 Such, procedure;and arrangement for inject-i ing liquids is,of course, iconventional;

required to dissipate heat of reaction; thus,; it] there is atemperature drop without the 11SefQf cooling waterv or equivalent, or ifthere is no rise in temperature without using cooling water control,careful investigation should be made.

The resins employed are prepared in the'manjner described in our saidPatent 2,560,333, and" the resins are identified hereafter in termed thezg example numbersiof that patent. Instead of be-f ratio, but alsofrom-- 2. standpoint of adding one 1 oxide first and thenthe other, andalso from the standpoint of adding both oxides simultaneously. Thiscan-be-doneconveniently in lightof what has been saidpreviously.

From a practical-standpoint, usingpilot-plant' equipment, for: instance,I aneautoclave having 7 a capacity of approximatelyfito- 5 gallons,- wehave made a single run by appropriateselections in which the molaliratioof resin equivalent to ethylene oxide is one toone, l to.- 5, l to- 10,'1 to 15, and Ito 20, or theisame-r'atios using propyl ene oxide,followed. by addition of the other oxides. through. asomewhat similar.range, i. e.,

1 to 20 moles of propyleneoxide. after. the initial addition of ethyleneoxide, or lto 20- moles, of

pressure of the ethylene oxide was sufficiently great to pass into theautoclave, or Wehave usedan arrangement, which, in essence, wastheequivalent-of an ethylene-oxidecylinder with a means for injectingnitrogen; so as; to ,forcethe; ethylene oxide in, the:,manner of anordinary: seltzer bottle, combinedwith the meansafor either:

weighing the-cylinder or measuring the ethylene oxide usedvolumetrically. -In the case 'of pro pylene oxide we invariably usednitrogen pres theobv ious text, where reference-is madeto the ingprepared on'a laboratory" scale, there were; prepared in'10 to1'5'-gallon electro-vapor-heated snythetic resin pilot plant reactors,as' maiiufactured by the Blaw-Knox Company, Pittsburgh,

Pennsylvania, and completely describedin their" Bulletin No. 2,087,issued in .1947, with'specific' reference to Specification No.715-3965;"

Inpreparing the derivatives we have usedfthe following f procedure;throughout. Prepare? the resins with a certain amountjofsolvent',such'asf 1 xylene, present purely as a convenience we" have treated theresins; withpropylene oxide and etliylene'oxide in threetdifferent ways:p

(a). Add the ethylene oxide first and: then the" v propyleneoxide; I H 71 Add-the; p opy ene oxide first and thenf the ethylene oxide; and

(0,), Use a mixture of propylene oxide and ethylene oxide, and make asingle addition.

' In each, case. we have used an alkaline catalyst equivalent; toapproximately one-half to"1;% of the total reaction mass in the finalstage, or equivalent, to one-fourth percent. of alkaline catalyst basedon final compound. ,In some cases, as is 'obyi'ous, such materials wouldbe' made step-wise for; thereason thati'it is more:

convenient. to produce abatch of oxypropylated resin,fsplit, 'i t intothree parts, forinstance, and? treat it with, threedifierent..ratios,.of :propy1enef i U oxide; or,. ihversely,,prepare anoxy'propyl'at'edi resin and splitit. into three batches and ti'e'at,ii';. with various amounts: of ethylene oxide. Briefly stated theinitial exploration was based on the}; combined deriy-atiyes. previouslymentioned .-intheearlier-part of; thistext. -Further exploration wasbased ongpreparingrthe followinglcompoundsw ient to operaterandaseii'thelimitscn-iagiweightt basis. 1 H 1 V Reference to. molalib'asi's. means'the phenolic;

nucleus, plus a: single: adjoiningsbridgey i& e, the? structural unit:-or, stated anothepwa'y, the radi i cal attached- 1th eachphenolichydroxyl. This? reference to a'mol'al ratio-is-distinguished from i e.,a molecule consisting of several structural- Propylene Ethylene Solvent,Resin Oxide Oxide Per cent 1 2 2 50. O 1 2 4 50. O 1 2 7 50. 1 2 10 50.0 1 3. 2. 5 50. 0 1 3, 5 4. 7 50. 0 1 3. 5 7 50. 0 1 3. 5 50. 0 1 3. 550. 0 l 6 3 50. 0 1 5 6 50. 0 1 5 9 50. 0 1 5 12 50. O 1 5 15 50. 0 1 83 50. 0 1 8 6 50. l) 1 8 9 50. 0 1 8 12 50. 0 1 8 15 50. 0 1 14 3 50. 01 14 6 50. 0 1 14 .9 50. 0 1 14 12 50. 0 1 14 15 50. 0 1 14 18 50. 0 114 21 50. 0

In each case a number of resins were employed. In fact, the bulk of theinvestigation was based on seven resins obtained by the action ofacetylene on the following seven phenols:

1. Para-secondary butylphenol 2. Para-tertiary amylphenol 3.Para-phenylphenol 4. Para-octylphenol '5. Mixed paraandortho-propylphenol 6. Cardanol 7. Side-chain hydrogenated cardanol ents.Points in the area represent composition indicated in the usual manner.

Briefly stated, exploration revealed that the most effectivecompositions, from the standpoint of demulsification, and for thatmatter, for other purposes, were found within the area approximatelydefined by the tetrahedron whose points are I, 2, 3 and 4. Within thistetrahedral area compounds whose compositions are found approximatelywithin the parallelogram defined by points 3, I, 5 and 6, were foundmost efiective. 'The second most effective class of materials, from thestandpoint of demulsification, were found within the tetrahedral areadefined approximately by points 5, 8, 9 and 6.

The determining points in the large tetrahedron r 1,2, 3 and 4,'areindicated in the following data,

both on a weight basis and a molal ratio basis. Obviously, the weightbasis is more satisfactory,

because as difierent resins are employed the :formulations for change inmolecular weight of the resin unit are eliminated, to say nothing ofthease 'ofproducing'the desired compounds, by

"merely following predetermined weight ratios dicated by the graph.

Propylene Oxide Per cent Per cent Per cent 60 30 10 A series of 9oxyalkylated derivatives were made from the first five resins in thelist above, i. e., para-secondary butylphenol, para-tertiary amylphenol,para-phenyl phenol, para-octylphenol, and mixed paraandoctylpropylphenol. This particular series again was made incomparatively small amounts. In preparing these compounds We used a verysmall laboratory autoclave which handled approximately 15 to 50 grams ofmaterial as a starting point. In each instance the amount of solvent wasadded so that the final product, after the completion of theoxyalkylation step, represented fifty percent solvent. The solventemployed was xylene.

The following table shows the exact amount of materials employed, i. e.,weight of resin employed, weight of ethylene oxide employed, weight ofpropylene oxide employed, total amount .of solvent present in thereaction mass, and also the amount of flake caustic soda employed as acatalyst.

Flake Point Ethylene Propylene Wt. of Ex. No. on ffjg Oxide, Oxide,Xylene,

Chart Grams Grams Grams G rams 1 (i0 30 10 100 5 5 50 40 10 100 5 8 3060 10 100 5 2 10 215 25 250 1. 0 9 10 150 90 250 1. 0 6 10 250 1. O 3 1O25 215 250 1.0 7 50 10 40 100 5 4 60 10 30 100 5 As stated, this serieswas made on a small laboratory scale from five differentphenol-acetylene resins, i. e., butylphenol, amylphenol, phenylphenol,octylphenol and propylphenol. In each case 45 derivatives were made inthree different ways:

(a) Adding all the ethylene oxide first and then propylene oxide;

(1)) Adding all propylene oxide first and then ethylene oxide;

(0) Mixing the two oxides and adding them simultaneously.

We have prepared also a number of similar derivatives in which thepreviously mentioned seven resins prepared from a selected phenol andacetylene were given an after-treatment with an aldehyde so as toproduce a more complex resin in which there was present more than onetype of linking unit, i. e., one derived from acetylene and one derivedfrom an aldehyde. The same applies to some resins which were prepared ina reverse manner, in which the phenol-aldehyde resin was subjected toafter-treatment with acetylene.

In our two co-pending applications Serial Nos. 129,707 (now Patent No.2,557,081, dated June 19, 1951) and 129,708, filed November 28, 1949, wepointed out that resins derived exclusively from phenols, as specifiedtherein, and formaldehyde, react the same Way in the ethyleneoxide-propylene oxide treatment, as do resins 4 235714; l5-1derived2exclusively .from .comparablemh-enolseand acetylene. Itfollows obviously: that such;,resins in which the mixed groupingsappear, i. e., both acetylene groupings and. aldehyde groupings, mustfall within the same limiting characteristic, and for this reason andfor purpose 'of brevity, .the rest of the; description will beconcerned. largely with the; phenol-acetylene resins, although the mixedtyperesin acts substantially the same and is susceptible to. the sametreat-i110 ment, as, f-aras oxyalkylationgoes, with the same results.Weagain desire to point out that the amount of'alkaline catalyst used isnot critical. 'Ihis is.,.true, whether the catalyst becaustic soda,e

caustic potash, sodium methylategor any other suitable catalyst. j The.amountwhich ,weregularly employed has varied from.l%, based. onthe resinalone, to 1%, based ,onthe resin andoxides, although in many cases. thereaction has .beeno .speededf by using approximately. twice, ,thisamount of caustic. We are inclined tojbelieve that whenever the amountofcaustic represents more than 2% of the reactants present, ignoring inertsolvent, that, there may be some tendeincye to form cyclic polymers withthe alkylene oxide, .although this is purely a. matter of, speculation.For this reason, whether justified or not, we have j usually avoided useof excess amounts of catalyst.

' Referring nowhtothe. earlier reference .as tor the most suitablecombinations, it will be, noted, as previously stated, that they fallnot only within the trapezoidal area defined by points I, 2, 3 and 4, onthe accompanyin drawing, but more specificially within the parallelogramwhich, represents part of; the trapezoidal area. This parallelogram isdefinedjapproximately by points 5, 6, 3 and 1. We have prepared a largenumber of derivatives: which come within this preferred area, i. e.,within the: area of the parallelogram, and since such derivatives arethe most efiective demulsifiers, and also most; effective for otherpurposes, we &are including these ;data inconsiderable detail. It isunderstood, of course, in reach instance the composition is based; on.the 45 assumption that-the percentage by. weight basis is on astatistical basis, which it obviously must :.be, ,and-;assumescompleteness of reaction; This 7 applies," of course, not ;onlyto:.these1:examp1es, but also to all previous examples. .In;-.preparingthese; examples .zwey-have -;used a xylenesolution obtained bydissolving the resin. 1-The fina -l.-prodeuct in. all instances wasadjusted to 50% xylene and 50% resin. This was purely. a .ma;tter=of.convenience. i;.1n thisparticular series, .-'.and, in, fact, any otherseries where large-ia'mounts of akphenol resin weresaemployedywe have.used :-.commercially available para-tertiary butylphenol acetylene:resin.; The amounts of- 1o.ther. resins availablewerewlimited, andthus, p-artof-the exqperimentszwere conducted: on a laboratory scale.-The resins employed inthe iirsteseries of compounds which areidentified as Examples :XAAl, through and including XFFl, were obtainedfrom amylphenol acetylene resins,:=andr which,-. for; all i practical..pl l poses..iarei .nothing; mor.eetharr the amylphenoli{11011101081163} of: ;the commercially available butyl. acetylene resin.The amount? of .zesin; ..empl0yed'.r:.the;zamount oiatethylene oxideemployed; and the amount oipropyleneoxide employed," are given;in;,grams in; thieziollowing six -.,examples. :The .weight ofcausticsoda employed is indicated in.,grams. In all .theseexamples, allpropylene. oxide. Was addedv first .and. :then all ethylene oxide.

Ethylene Propylen .i lake ;Ex. No. 3 Oxide Oxide Gaustic m Gra ge cam62. 4 32. 5 42.0 7s a 45,7 35. 0 v75. 0 75 a4. 5 25. 0 90. 5 31.4 25; 0144:. 8 1. 0

the subsequent resins were the same analogues 1 of commercialbutylphenol acetylene resins, except that the other phenols wereemployed as previously-noted, and. as herein specified. f

For. example, in the third series of, six compounds the same ratios wereused and identified, 1 The resin T as Examples XAA3, throught XFF3.employedwas prepared from acetylene and paraphenylphenol.

A fourthseries of six examples were prepared, us the s er andi ea ifi q...E a ple XAA4, through XFFe, and prepare pararoctylphenol.

Similarly, a t seri s wa nre a d r m th resin obtained by reactionbetween mixed paraand orthophenol sand. acetylene, designated .as

XAA5, through XFF5.

Likewise, a sixth series wasypreparedfiromithe only presentlycommercially-available;phenol the resin obtained from para-tertiarybutylphenol and acetylene-Koresin as sold in theiopenamarket. This lastseries :was indicated-..as:XAA6, throughXFfFii.

In all these seriesthesame ratios ofreaetants as indicated in ExamplesjXAAlthrough ,XE'Fl were used. The. procedure was the 7 same as ,hasbeen described previously in regard to oxyethyl- 'ation andoxypropylation- Ineachinstance the propylene oxide was. added first andthengthe ethylene oxide.

. In asecond. series. of thirty compoundsjthe same ratioswere preservedin everyr.respect', ex-

cept that, ethyleneoxide was added first and then propylene oxide.Theseseries are indicated. by the. designations YAAl', YBBl, 'YCCl,YDDl,

YEEl, and YFFl, for the .ainylphenols, and'the" correspondingdesignation for the others.

-, A third serieswas prepared, using the same ratios ,exceptthat.ethylene oxide. and prop lene oxidewere .mixed together. and addedsimultan'eby the prefix Zinstead of X and Y.

f. Examination oferesultsin demulsifioationgtests shows that the Xseries waswbes t, the Ya sifies f .very good,;and the .Z series good.

In the. .final' comparison an the. resinsavere on f-the oxyalk iated an,equaldilution basis, o derivatives and 50% xylene. f

:The oxyalkylation of a resin ot'the lrindherein described w th arr ne ye ec eda lkr ene o id V V will produce a ,material, which, ifpxyallgylation his eXteniye-.9e934sh.-. her inesrqlea i ro olub eiin beemployed as diluents. such as pine oil, carbon tetrachloride, sulfurdioxide extract obtained in the refining of pewater, so that a dilutesolution, for instance, 1%

in water at 22.5 C. in an ordinary test tube of approximately one-halfinch thickness, produces a solution or sol which is transparent to theeye. Needless to say, this does not apply to any alkylene oxide. Forinstance, the reaction product of y a mole or a few moles of phenylethylene oxide with a water-soluble product, yields a waterinsolubleproduct. Even water willserve to illustrate this change in property.Treatment of a resin with sufficient ethylene oxide will produce aproduct having the characteristics noted and 'which apparently show atleast some detersive .where in between these two limits, i. e., it maysuspend in water as an opaque colloidal sol, or may perhaps not do quitethis well, or perhaps even better, but in any event, does not give aclear solution when tested in the manner previously indicated, and does'not have any detersive properties. 'All the products which we haveexamined which come within the parallelogram on the graph indicated bypoints 5, 6, 3 and 7, are

of this semi-soluble or non-detersive type.

When a hydroxylated material is subjected to oxyalkylation, particularlyin such instances .where a plurality of moles of the alkylene oxide areused per hydroxyl, one does not obtain a compound but a mixture, which,on a statistical basis, corresponds to the predetermined ratios.

Conventional demulsifying agents employed in the treatment of oil fieldemulsions are used as such, or after dilution with any suitable solvent,

such as water, petroleum hydrocarbons, such as benzene, toluene, xylene,tar acid oil, cresol,

anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such asmethyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butylalcohol, hexyl alcohol, octyl alcohol, etc., may Miscellaneous solventstroleum, etc., may be employed as diluents. Similarly, the material ormaterials employed as the demulsifying agent of our process may be'adm'ixedwith one or more of the solvents customarily used in connection'with conventional demulsifying agents. Moreover, said material ormaterials may be used alone or in admixture with other suitablewell-known classes of demulsifying agents.

It' is well known' that conventional demulsifyand water is notsignificant because said reagents undoubtedly have solubility withinsuch concentrations. This same fact is true in regard to the material ormaterials employed as the demulsifying agent of our process.

The present invention is concerned with treatment of petroleum emulsionsby means of certain oxyalkylated resins which are hydrophile orsub-suri'aceor surface-active. Such resins, in turn, areoxyalkylation-susceptible, waterinsoluble, organic solvent-soluble,fusible phenolic resins, obtained, in part, at least, by the use of anacetylenic hydrocarbon and derived from difunctional or other suitablephenols. Based on actual large scale application in a large number ofoil fields in the United States and certain foreign countries, webelieve that this type of material, either as such or in the form ofderivatives, will ultimately be employed in no less than 50% of allchemical demulsifying agents used throughout the world.

In practising our process for resolving petroleum emulsions of thewater-in-oil type, a treating agent or demulsifying agent of the kindabove described is brought into contact with or caused to act upon theemulsion to be treated, in any of the various apparatus now generallyused to resolve or break petroleum emulsions with a chemical reagent,the above procedure being used alone or in combination with otherdemulsifying procedure, such as the electrical dehydration process.

One type of procedure is to accumulate a volume of emulsified oil in atank and conduct a batch treatment type of demulsification procedure torecover clean oil. In this procedure the emulsion is admixed with thedemulsifier, for example by agitating the tank of emulsion and slowlydripping demulsifier into the emulsion. In some cases mixing is achievedby heating the emulsion while dripping in the demulsifier, dependingupon the convection currents in the emulsion to produce satisfactoryadmixture. In a third modification of this type of treatment, acirculating pump withdraws emulsion from, e. g., the bottom of the tank,and re-introduces it into the top of the tank, the demulsifier beingadded, for example, at the suction side of said circulating pump.

In a second type of treating procedure, the demulsifier is introducedinto the well fluids at the well-head or at some point between thewellhead and the final oil storage tank, by means of an adjustableproportioning mechanism or proportioning pump. Ordinarily the flow offluids through the subsequent lines and fittings sufiices to produce thedesired degree of mixing of demulsifier and emulsion, although in someinstances additional mixing devices may be introduced into the flowsystem. In this general procedure, the system may include variousmechanical devices for withdrawing free water, separating entrainedwater, or accomplishing quiescent settling of the chemicalized emulsion.Heating devices may likewise be incorporated in any of the treatingprocedures described herein.

A third type of application (down-the-hole) of demulsifier to emulsionis to introduce the demulsifier either periodically or continuously indiluted or undiluted form into the well and to allow it to come to thesurface with the well fluids, and then to flow the chemicalized emulsionthrough any desirable surface equipment, such as employed in the othertreating procedures. This particular type of application is decidedlyuseful when the demulsifier is used in connection with acidification ofcalcareous oil-bearing strata, especially if suspended in or dissolvedin the acid employed for acidification.

In all cases, it will be apparent from the foregoing description, thebroad process consists simply I in- I introducing a --relati velysmallproportion of demulsifien-into arelatively large proportion of emulsion;admixingthechemical and emulsion either through natural II flow orthrough special apparatus, with --orwi-thout the application -f heat,andallowing-themixture to stand quiescent until the undesirable Watercontent of the emulsion 'separates and settles from the mass.

The followingis I a typical installation: I

A reservoirto hold-the demulsifier of the-kind described -(di1uted orundiluted) is placed at the well-headwherethe-efiluent liquids leave thewell. This reservoir ole-container; which mayvary from gallons to 50gallons for-convenience,-is-connected' to a proportioning pump whichinjectsthe demulsifierdrop-wise intothe fluids leaving the well. Srchchemicalized' fiuidepass throughthe flowline into a settling tank. Thesettling'tank consists of a, tank of anyconvenient-size,-forin- 1stance, one which 'willhold amounts of' fiuid-produced in 4 to Z lhours(500 barrels-to 200O'barre1s capacity) ,and in which there is-aperpendicular conduit mm thetop of the tank te -almostthe ,very bottomso as to permit the incoming fluids to pass from the top of the settlingtank-tmthe bottom, so that such incoming fluidsdo notdisturbstratification which takes-place duringthe course ofdemulsificationz The settling tank has two 'outlets, one being belowthe-water level-to"- drain offthe water-resulting from demulsificationor-accoripanying the emulsion as'freewater, the other being anoil outletatthe top to permit" the passage of dehydratedoil toasecond tank, be-

ing a storage tank' which holdspipeline or de- I hydrated-oil;- Ifdesired; the conduit-or pipe which serves to carrythe-fluids from theWell to the-settling tank may include-a section-*ofpipe with baffles toserve as am-ixer,'- toinsure thorough distribution of the-demulsifierthroughout the fluids, or-a heater for -raisingthetemperature of the fluids to some convenient temperature, for instance,120 to 160 F;-,-or-both--heater and mixer.

Demulsification procedure is started by simply setting the pump- 'soasto feed a comparatively large" ratio of demulsifier; for-instance; 1 :5,OOO. As soon asa complete break or' satisfa'ctory demulsificationisobtained,-"the--pump isregulated until experience shows that" the-amount of' demulsifier beingaddedis just-"suflicientto produce clean ordehydrated oil. The-"amount beingfed at such stage is' usually 110,000,1:15-,000, 1:20,000, or the like.

In many instances the oxyalkylated products herein specified asdemulsifiers can be'conveni'ent- 1y used without dilution. However, aspreviously noted, they m'ayibeidiluted as' 'desiredwith' any suitablesolvent. For instance, by mixing .75 parts by Weight of an oxyalkylatedderivative, forexample, the product of Example XAAQpwith parts by weightof Xylene and 10 parts by weight of isopropyl alcohol, an excellentdemulsifier-is obtained. Selection of the solvent.,wil1-vary,.-,de.-pending upon the solubility characteristicsofithe oxyalkylated product,and of course,*.will;be :dictated, in part, by "economicconsiderations,i. e.,

cost. I

As noted above, the products-herein described may be used not only indiluted 'form;but alsomay be used admixed with some other chemical"demulsifiers. 7

An illustrationis the use ofa mixture comprismg:

Oxyalkylated derivative; for example the prod I not of Example XAAG,

A -cyclohexylamine salt of a polypropyla'ted A sodium salt of 'oilsoluble mahogany petro A :high-boiling aromatic petroleum solvent,

Isopropyl alcohol; 5%

The above proportions are all Weight percents; V The instantapplicationie concerned withthe.

use of oxyalkylated resinous compounds-"or derivatives'-thereoffordemulsification of petroleum emulsiohsof the water in-oil type. It isobvious that I the alicy'clic analogues. derived bynuclear hydrogenationI 'are-'= equa1ly serviceable for 1-. this purpose, and particularlyasintermediates for the manufacture of more: complex compoundsfor use asdemulsifying agents. -In' :a -general way conversion of the aromaticmaterial to an alicyclic material follows eitherfo'ne' or twoprocedures: One can hydrogenate the resin in a conventional.mannergfollowedby'oxyalkylation ofthe hYdro- .genate'd' resin -insubstantially the same -manner as 1. is I employed in-"thecase of thernon-hydrogenated: resin- The second procedureis tohy drogenate theoxyalkylated derivative, rathe than the resin itself; I

Having thus I. described our invention; What we claim as new anddesireto secure by LettersfPat- 1. A "process for breaking petroleum'emulsions .offthe water-in-oil ty-pe, characterized by subjecting theemulsion to the' acti'ozr of a demulsifier-ineluding hydrophilesynthetic products; said hydrophile synthetic products beingoxyalk-ylation products of (a)- Both ethylene oxideandpropylene oxide;and b) I An oxyalkylation -susceptible,

fusible, organic solvent-soluble, water=in soluble phenolic resin; saidresin being gderived" at least in part by I reaction" with anacetylene'hydro'carbon so-asto introduce "an-alternate acetylenicradical as the-linkingstructure between phenolic nuclei;- saidoxyalkylated' resin being characterized by the introduction into :theresin molecule of a plurality of divalent (321- findCzH's'Q' radicals,with the-proviso that the compositionof said hydrophile syntheticproducts;based on a statise tical average and assuming completeness ofreaction, and calculated "backto 'the threetoxyalkylation stepreactants, i; e., resin, ethylene oxide'and propylene oxide, "onepercentage weight basis must fall approximatelywithin the area "definedby the trapezoid l,' 2, 3 and"fi on'ithe accompanying drawing; andwiththe'final provisdthat' the hydrophile properties. of. saidoxyalkylated resin in an equal weight ofxylene'are sufficient toprodu'cean emulsion'when' said xylene solution is. shaken vigorously with oneto'threeycilumes of water. II W 2. A process for breaking gpetroleu'm'"emulsions of the WatGIEFiII-DlI type, characterized by sub jecting'theemulsionto the action of 1a.'dem'u1sifier .including .hydrophil'e:synthetic products; said 'hydrophile synthetic. products being.oxyalkyla;

tion products of .(a) Both 'eth'yleneoxide and.

propylene oxide; and f (b) An. oxya1k'ylation-sus+ ceptible, fusible,organic .solventejsolublewaterrinsoluble phenolic resin; said resin beingI..der-ived by'reactionwith an .acety1enehyd-rocarbon so as theintroduction into the resin molecule of a plurality of divalent C2H4Oand CsHeO radicals, with the proviso that the composition of saidhydrophile synthetic products, based on a statistical average andassuming completeness of reaction, and calculated back to the threeoxyalkylation step reactants, i. e., resin, ethylene oxide and propyleneoxide, on a percentage weight basis must fall approximately within thearea defined by the trapezoid l, 2, 3 and 4 on the accompanying drawing;and with the final proviso that the hydrophile properties of saidoxyalkylated resin in an equal weight of xylene are sufiicient toproduce an emulsion when said xylene solution is shaken vigorously with1 to 3 volumes of jecting the emulsion to the action of a demulsifierincluding hydrophile synthetic products; said hydrophile syntheticproducts being oxyalkylation products of (a) Both ethylene oxide andpropylene oxide; and (b) An oxyalkylation-susceptible, fusible, organicsolvent-soluble, water-insoluble phenolic resin; said resin beingderived by reaction with acetylene so as to introduce an alternateacetylenic radical as the linking structure between phenolic nuclei;said oxyalkylated resin being characterized by the introduction into theresin molecule of a plurality of divalent C2H4O and CaHsO radicals, withthe proviso that the composition of said hydrophile synthetic products,based on a statistical average and assuming completeness of reaction,and calculated back to the three oxyalkylation step reactants, namely,resin, ethylene oxide and propylene oxide, on a percentage weight basismust fall approximately within the area defined by the trapezoid, I, 2,3 and 4 on the accompanying drawing; and with the final proviso that thehydrophile properties of said oxyalkylated resin in an equal weight ofxylene are sufficient to produce an emulsion when said xylene solutionis shaken vigorously with 1 to 3 volumes of water.

4. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifierincluding hydrophile synthetic products; said hydrophile syntheticproducts being oxyalkylation products of (a) Both ethylene oxide andpropylene oxide; and (b) An oxyalkylation-susceptible, fusible, organicsolvent-soluble, waterinsoluble phenolic resin; said resin being derivedby reaction with acetylene so as to introduce an alternate acetylenicradical as the linking structure between phenolic nuclei; saidoxyalkylated resin being characterized by the introduction into theresin molecule of a plurality of divalent CzH4O and CaHsO radicals, withthe proviso that the composition of said hydrophfle synthetic products,based on a statistical average and assuming completeness of reaction,and calculated back to the three oxyalkylation step reactants, i. e.,resin, ethylene oxide and propylene oxide, on a percentage weight basismust fall approximately within the area defined by the parallelogram 5,6, 3 and I on the accompanying drawing; with the final proviso that thehydrophile properties of said oxyalkylated resin in an equal weight ofxylene are sufficient to produce an emulsion when said xylene solutionis shaken vigorously with 1 to 3 volumes of Water.

5. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifierincluding non-detersive hydrophile synthetic products; saidnon-rdetersive hydrophile synthetic products being oxyalkylationproducts of (a) Both ethylene oxide and propylene oxide; and (b) Anoxyalkylation-susceptible, fusible, organic solvent-soluble,water-insoluble phenolic resin; said resin being derived by reactionwith acetylene so as to introduce an alternate acetylenic radical as thelinking structure between phenolic nuclei; said oxyalkylated resin beingcharacterized by the introduction into the resin molecule of a pluralityof divalent C2H4O and CsHeO radicals, with the proviso that thecomposition of said non-detersive hydrophile synthetic products, basedon a statistical average and assuming completeness of reaction, andcalculated back to the three oxyalkylation step reactants, i. e., resin,ethylene oxide, and propylene oxide, on a percentage weight basis mustfall approximately within the area defined by the parallelogram 5, 6, 3and 1 on the accompanying drawing; and with the final proviso that thehydrophile properties of said non-detersive oxyalkylated resin in anequal weight of xylene are sufficient to produce an emulsion when saidxylene solution is shaken vigorously with 1 to 3 volumes of water.

6. The process of claim 5, wherein the resin is derived frompara-tertiary butylphenol '7. The process of claim 5, wherein the resinis derived from para-tertiary amylphenol.

8. The process of claim 5, wherein the resin is derived frompara-octylphenol.

MELVIN DE GROOTE. BERNHARD KEISER.

REFERENCE S CITED The following references are of record in the file ofthis patent:

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE,CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFERINCLUDING HYDROPHILE SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETICPRODUCTS BEING OXYALKYLATION PRODUCTS OF (A) BOTH ETHYLENE OXIDE ANDPROPYLONE OXIDE; AND (B) BOTH ETHYLENE OXIDE AND PROPYLFUSIBLE, ORGANICSOLVENT-SOLUBLE, WATER-INSOLUBLE, PHENOLIC RESIN; SAID RESIN BEINGDERIVED AT LEAST IN PART BY REACTION WITH AN ACETYLENE HYDROCARBON SO ASTO INTRODUCE AN ALTERNATE ACETYLENIC RADICAL AS THE LINKAGE STRUCTUREBETWEEN PHENOLIC NUCLEI; SAID SAID OXYALKYLATED RESIN BEINGCHARACTERIZED BY THE INTRODUCTION INTO THE RESIN MOLECULE OF A PLURALITYOF DIVALENT C2H4O AND C3H6O RADICALS, WITH THE PROVISO THAT THECOMPOSITION OF SAID HYDROPHILE SYNTHETIC PRODUCTS, BASED ON ASTATISTICAL AVERAGE AND ASSUMING COMPLETENESS OF REACTION, ANDCALCULATED BACK TO THE THREE OXYALKYLATION STEP REACTANTS, I.E., RESIN,ETHYLENE OXIDE AND PROPYLENE OXIDE, ON A PERCENTAGE WEIGTH BASIS